Iodine perchlorates

ABSTRACT

Iodine perchlorates of the formula X(OClO3)n wherein X is selected from the group consisting of I and CsI 4, wherein n equals 3 when X is I and n equals 4 when X is CsI 4, are prepared by reacting ClOClO3 with either solid I or CsI at low temperatures. The iodine perchlorates are useful as energetic oxidizers.

United States Patent [191 Christe et al.

[ IODINE PERCHLORATES [75] Inventors: Karl O. Christe, Calabasas; CarlJ.

Schack, Chatsworth, both of Calif.

[73] Assignee: The United States of America as represented by theSecretary of the Navy, Washington, DC.

22 Filed: May 24,1973

211 App]. No.: 363,708

[ Mar. 25, 1975 [56] References Cited UNITED STATES PATENTS 3,694,1729/1972 Schack et a]. 423/466 Primary ExaminerEdward Stern Attorney,Agent, or Firm*R. S. Sciascia; J. A. Cooke [57] ABSTRACT Iodineperchlorates of the formula X(OClO;,),, wherein X is selected from thegroup consisting of 1 and Csl, wherein n equals 3 when X is l and )1equals 4 when X is Csl, are prepared by reacting 'ClOClO with eithersolid 1 or Csl at low temperatures. The iodine perchlorates are usefulas energetic oxidizers.

5 Claims, N0 Drawings IODINE PERCI-ILORATES BACKGROUND OF THE INVENTIONThis invention generally relates to perchlorate compounds and moreparticularly to iodine perchlorates.

The alleged preparation of iodine trisperchlorate from iodine, ozone,and anhydrous HCIO is described by M. Schmeisser in Handbook ofPreparative Inorganic Chemistry, G. Brauer, Ed., Academic Press, NewYork, N. Y. 1963, Vol. 1, pg. 330. However, a crosscheck with theoriginal publication, F. Fichter and H. Kappeler, Z. Anorg. Allgem.Chem., 91, 134 (1915), reveals that the original paper deals only with acompound having the empirical composition, 1(- ClO,) 2H O. Further, fromthe properties of 1(0- C1O it appears unlikely that the Fichter, et211., compound was the bishydrate of I(OClO The bishydrate of iodinetrisperchlorate, I(OClO 21-1 0, should be a less energetic oxidizer thanthe anhydrous form, and therefore would be less suitable forpropellants. In view of this attempts have been made to obtain thebishydrate as well as the anhydrous material.

SUMMARY OF THE INVENTION Accordingly, one object of this invention is toprovide iodine perchlorates.

Another object of this invention is to isolate iodine perchlorates inthis solid anhydrous form.

A further object of this invention is to provide iodine perchlorateswhich are highly energetic oxidizers.

A still further object of this invention is to provide a method ofsynthesizing iodine perchlorates.

Still another object of this invention is to achieve a high degree ofpurity in the iodine perchlorates synthesized.

Yet another is to provide a easy means for purifying the iodineperchlorates.

These and other objects of this invention are accomplished by providingcompounds which are iodine perchlorates of the formula X(OC10 wherein Xis selected from the group consisting of 1 and Csl wherein n equals 3when X is 1*, and n equals 4 when X is Csl. The iodine perchlorates areprepared by reacting chlorine perchlorate, ClOClO with a substanceselected from the group consisting of 1 and Csl at low temperatures.

DESCRIPTION OF THE PREFERRED EMBODIMENT The iodine perchlorates of thisinvention are prepared by reacting chlorine perchlorate, CIOCIO witheither iodine, 1 or Csl. The reaction for preparing iodinetrisperchlorate is as follows:

1 6ClOC1O 2l(OClO b 3Cl and the reaction for preparing the cesiumtetraperchlorato iodate is as follows:

The range of suitable reaction temperatures is limited by the slowreaction rates and the instability of the iodine perchlorate products.For examle, the iodine trisperchlorate reaction takes 70 hours at --50Cand the cesium tetrapherchlorato iodate reaction takes weeks at 31 45Cto go to 99 percent completion and at lower temperatures the reactiontakes still longer. On the other hand, while the Csl(OClO is stable at23C, io-

2 dine trisperchlorate rapidly decomposes, at this temperature. 1

Thus, the reaction temperature for producing Csl(O- C10 should be in therange 78 to 30C, preferably 55 to 40C; and the reaction temperature forproducing iodine trisperschlorate should be in the range 78 to 0C,preferably 55 to --40C.

Purification of the product is simplified by reacting a stoichiometricexcess of chlorine perchlorate with iodine or cesium iodide in an inertenvironment. The excess of chlorine perchlorate is used to drive thereaction to 99 percent completion. The the solid I(OClO or Csl(OC|Oproduct can be separated from the byproduct chlorine and unreactedchlorine perchlorate at low temperatures under vacuum. Finally, sincewater is neither a reactant nor a product in either of the reactions,the anhydrous form of l(OC1O or CsI(OClO is obtained when the reactionis run in an anhydrous environment. Additionally, because of thereactivity of the desired perchlorates it is most desirable to conductthe reactions in an inert environment which, within the context of thisinvention, is meant to include anhydrous conditions.

The general nature of the invention having been set forth, the followingexamples are presented as specific illustrations thereof. It will beunderstood that the invention is not limited to these specific examplesbut is susceptible to various modifications that will be recognized byone of ordinary skill in the art.

EXAMPLE 1 Iodine Trisperchlorate l( OCIO Iodine (0.915 mmol) was loadedinto a 10 ml prepassivated Teflon FEP ampoule closed off by a stainlesssteel valve. Chlorine perchlorate (8.18 mmol) was added at l96C. Theampoule was kept at -50C for hours. At this point, the dark iodine colorhad disappeared and a pale yellow (due to the presence of C1 solid hadformed. Upon cooling to 196C, the ampoule did not contain anynon-condensible reaction products. The ampoule was slowly warmed to 45C.The volatile products were separated by fractional condensation andidentified by infrared spectroscopy and their vapor pressure. Theyconsisted of C1 (2.70 mmol) and ClOClO (2.74 mmol). The white, solidresidue weighed 776 mg., in excellent agreement with the weight (777 mg)calculated for a complete conversion t0 EXAMPLE 2 CesiumTetraperchlorato Iodate (Ill) CsI(OClO A 10 ml prepassivated stainlesssteel cylinder was loaded with powdered anhydrous Csl (1.15 mmol),followed by ClOClO (6.10 mmol) at b l96C. The reaction was allowed toproceed by warming the cylinder to 45C, where it was maintained for 5weeks. On recooling to l96C, no non-condensible gases were observed.Volatile products were pumped from the reactor for several hours whileand after it had warmed to ambient temperature. Separation of thesespecies was affected by fractional condensation and identification byinfrared and vapor pressure measurements. They consisted of C1 (2.34mmol) and unreacted ClOClO (1.45 mmol). The solid product was paleyellow in 3 4 color and weighed 749 mg, indicating a 99 percent conof78C to 30C for 70 or more hours, provided version of the CsI to Csl(OC|O had occurred. that at least 4 moles of chlorine perchlorate areObviously, numerous modifications and variations of used per mo|e fCesium did the present invention are possible in light of the above Themethod of claim 1 wherein Said Contacting is teachings. It is thereforeto be understood that within performed at a temperature of to Q thescfope of the aPpended clalms .nventlon be 3. The method of claim 1,wherein more than 4 moles practiced otherwise than as specificallydescribed herein. of said chlorine perchlorate IS used per mole ofcesium What is claimed as new and desired to be secured by IodideLetters Patent of the United States is: 4. Cesium tetraperchloratoiodate (Ill), Csl(OC 3).

l. A method of preparing cesium tetraperchlorato as Produced y the P ofclam iodate (III), Csl(OClO comprising: 5- The product of claim 4,wherein the said iodute contacting chlorine perchlorate and cesiumiodide in compound is anhydrous.

an inert environment at a temperature in the range

1. A METHOD OF PREPARING CESIUM TETRAPERCHLORATO IODATE (III),CSI(OC1O3)4, COM CONTACTING CHLORINE PERCHLORATE AND CESIUM IODIDE IN ANINERT ENVIRONMENT AT A TEMPERATURE IN THE RANGE OF -78*C TO 30*C FOR 70OR MORE HOURS, PROVIDED THAT AT LEAST 4 MOLES OF CHLORINE PERCHLORATEARE USED PER MOLE OF CESIUM IODIDE.
 2. The method of claim 1 whereinsaid contacting is performed at a temperature of -55*C to -40*C.
 3. Themethod of claim 1, wherein more than 4 moles of said chlorineperchlorate is used per mole of cesium iodide.
 4. Cesiumtetraperchlorato iodate (III), CsI(OCl3)4, as produced by the process ofclaim
 1. 5. The product of claim 4, wherein the said iodate compound isanhydrous.